EP0309711A1 - Verfahren zur Herstellung von Anilinofumaraten - Google Patents
Verfahren zur Herstellung von Anilinofumaraten Download PDFInfo
- Publication number
- EP0309711A1 EP0309711A1 EP88113254A EP88113254A EP0309711A1 EP 0309711 A1 EP0309711 A1 EP 0309711A1 EP 88113254 A EP88113254 A EP 88113254A EP 88113254 A EP88113254 A EP 88113254A EP 0309711 A1 EP0309711 A1 EP 0309711A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- anilinofumarate
- quinoline
- preparation
- aniline
- chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 33
- XQRVITDMGTWTIC-VURMDHGXSA-N (Z)-2-anilinobut-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)/NC1=CC=CC=C1 XQRVITDMGTWTIC-VURMDHGXSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 27
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 26
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000003444 phase transfer catalyst Substances 0.000 claims description 9
- XSCRWBSKSVOZOK-UHFFFAOYSA-N 2,3-dichlorobutanedioic acid Chemical compound OC(=O)C(Cl)C(Cl)C(O)=O XSCRWBSKSVOZOK-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 3
- 125000005208 trialkylammonium group Chemical group 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 2
- 239000011736 potassium bicarbonate Substances 0.000 claims 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims 1
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 claims 1
- DHAWHVVWUNNONG-UHFFFAOYSA-M tributyl(methyl)azanium;bromide Chemical compound [Br-].CCCC[N+](C)(CCCC)CCCC DHAWHVVWUNNONG-UHFFFAOYSA-M 0.000 claims 1
- 239000000543 intermediate Substances 0.000 abstract description 3
- SHLFJVZPNLKZRX-UHFFFAOYSA-N 2-(4,5-dihydro-1h-imidazol-2-yl)quinoline-3-carboxylic acid Chemical compound OC(=O)C1=CC2=CC=CC=C2N=C1C1=NCCN1 SHLFJVZPNLKZRX-UHFFFAOYSA-N 0.000 abstract 1
- 239000004009 herbicide Substances 0.000 abstract 1
- 235000017550 sodium carbonate Nutrition 0.000 description 13
- YHUVMHKAHWKQBI-UHFFFAOYSA-N quinoline-2,3-dicarboxylic acid Chemical class C1=CC=C2N=C(C(O)=O)C(C(=O)O)=CC2=C1 YHUVMHKAHWKQBI-UHFFFAOYSA-N 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 230000002363 herbicidal effect Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- PBGMSGHICSEALQ-UHFFFAOYSA-N diethyl 2,3-dichlorobutanedioate Chemical compound CCOC(=O)C(Cl)C(Cl)C(=O)OCC PBGMSGHICSEALQ-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical class [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 3
- QYAPHLRPFNSDNH-MRFRVZCGSA-N (4s,4as,5as,6s,12ar)-7-chloro-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC(Cl)=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O QYAPHLRPFNSDNH-MRFRVZCGSA-N 0.000 description 2
- RMHWTDKVSCTQHA-UHFFFAOYSA-N CCC(CC)(C(O)=O)C(Cl)C(O)=O Chemical compound CCC(CC)(C(O)=O)C(Cl)C(O)=O RMHWTDKVSCTQHA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- YTIVTFGABIZHHX-UHFFFAOYSA-N butynedioic acid Chemical class OC(=O)C#CC(O)=O YTIVTFGABIZHHX-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- QQVDYSUDFZZPSU-UHFFFAOYSA-M chloromethylidene(dimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)=CCl QQVDYSUDFZZPSU-UHFFFAOYSA-M 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- NLVZUORLSQCGFQ-UHFFFAOYSA-N furo[3,4-b]quinoline-1,3-dione Chemical class C1=CC=C2C=C3C(=O)OC(=O)C3=NC2=C1 NLVZUORLSQCGFQ-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- -1 quinoline imidazolinone compounds Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical class NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- QDXJFRHCHWDQSP-UHFFFAOYSA-N 1,4-dihydroimidazol-5-one;quinoline Chemical compound O=C1CNC=N1.N1=CC=CC2=CC=CC=C21 QDXJFRHCHWDQSP-UHFFFAOYSA-N 0.000 description 1
- PBHUSRBVKLAGGU-UHFFFAOYSA-N 2-carbamoylquinoline-3-carboxylic acid Chemical class C1=CC=C2C=C(C(O)=O)C(C(=O)N)=NC2=C1 PBHUSRBVKLAGGU-UHFFFAOYSA-N 0.000 description 1
- KLGHXRFGBQXCBN-UHFFFAOYSA-N 3-(4,5-dihydroimidazol-1-yl)quinoline-2-carboxylic acid Chemical class OC(=O)C1=NC2=CC=CC=C2C=C1N1CCN=C1 KLGHXRFGBQXCBN-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical class NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- ROMURMXNNUEGCC-BENRWUELSA-N diethyl (z)-2-anilinobut-2-enedioate Chemical compound CCOC(=O)\C=C(C(=O)OCC)/NC1=CC=CC=C1 ROMURMXNNUEGCC-BENRWUELSA-N 0.000 description 1
- JDXYSCUOABNLIR-UHFFFAOYSA-N diethyl 2-oxobutanedioate Chemical compound CCOC(=O)CC(=O)C(=O)OCC JDXYSCUOABNLIR-UHFFFAOYSA-N 0.000 description 1
- STRNXFOUBFLVIN-UHFFFAOYSA-N diethyl but-2-ynedioate Chemical compound CCOC(=O)C#CC(=O)OCC STRNXFOUBFLVIN-UHFFFAOYSA-N 0.000 description 1
- 229940071094 diethyl oxalacetate Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012035 limiting reagent Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- HJHUXWBTVVFLQI-UHFFFAOYSA-N tributyl(methyl)azanium Chemical compound CCCC[N+](C)(CCCC)CCCC HJHUXWBTVVFLQI-UHFFFAOYSA-N 0.000 description 1
- IPILPUZVTYHGIL-UHFFFAOYSA-M tributyl(methyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](C)(CCCC)CCCC IPILPUZVTYHGIL-UHFFFAOYSA-M 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/40—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino groups bound to carbon atoms of at least one six-membered aromatic ring and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
Definitions
- the present invention relates to novel methods for preparing anilinofumarates in order to prepare quinoline-2,3-dicarboxylic acids. These acids are useful intermediates in the preparation of herbicidal pyridine and quinoline imidazolinone herbicidal compounds.
- the herbicidal pyridine and quinoline imidazolinone compounds prepared from the present compounds include 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)quinoline-3-carboxylic acid, and esters and salts thereof and are disclosed in United States Patent 4,638,068, incorporated herein by reference.
- herbicidal imidazolinyl quinolinecarboxylic acids may be prepared by the procedure described in United States Patent 4,518,780 (incorporated herein by reference) by cyclization, under basic conditions, with an appropriately substituted 2-carbamoyl quinoline-3-carboxylic acid, that, in turn, is prepared by the reaction of a substituted quinoline-2,3-dicarboxylic acid anhydride and appropriately substituted aminocarboxamide or aminothiocarboxamide.
- Quinoline-2,3-dicarboxylic acid anhydrides are readily prepared from the diacids by procedures well known in the art. However, the diacids themselves are not readily available.
- ketoesters and dialkyl acetylene dicarboxylates such as diethyloxalacetate and diethyl acetylenedicarboxylate
- diethyloxalacetate and diethyl acetylenedicarboxylate is limited, thus restricting the quantities of anilinofumarate and quinoline-2,3-dicarboxylic acid, the intermediates required for preparing herbicidal 2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)quinoline-3-carboxylic acid, esters and salts thereof.
- United States Patent 4,675,432 describes a method for the preparation of anilinofumarates in which dichlorosuccinates are reacted with aniline in an organic solvent in the presence of aqueous base and a phase transfer catalyst in a temperature in the range of 20°C to 90°C for one to 24 hours.
- the present invention overcomes not only the limitations of providing a readily-available source of quinoline-2,3-dicarboxylic acid, esters and salts thereof but also provides an improvement in the reac tion of dichlorosuccinates with aniline resulting in significantly increased productivity and reduction in reaction times.
- an object of the present invention to provide an improved method for the preparation of anilinofumarates utilizing dichlorosuccinates, obtainable from readily available dialkyl maleates, and hence, an improved method for the manufacture of large quantities of quinoline-2,3-dicarboxylic acid and esters thereof and subsequent production of herbicidal 2-(4-isopropyl-4methyl-5-oxo-2-imidazolin-2-yl)-quinoline-3-carboxylic acid, esters and salts.
- the present invention relates to an improved method for preparing anilinofumarates and quinoline-2, 3-dicarboxylic acids and esters thereof.
- the method comprises reacting a dichlorosuccinate (formula I) with a molar equivalents of aniline and a minimum of two molar equivalent of aqueous base in the presence of a tri- or tetra-alkylammonium phase transfer catalyst at a temperature in a range of about 85°C to 100°C for about one to four hours in the absence of a solvent, and isolating the thus-formed anilinofumarate.
- Quinoline-2,3-dicarboxylate acid is then prepared from the thus-formed anilinofumarate by reacting the anilinofumarate with an approximately equimolar amount of a Vilsmeier reagent (immonium salt) in the presence of a hydrocarbon solvent such as toluene or a chlorinated hydrocarbon solvent such as methylene chloride, dichloroethane, ortho dischlorobenzene, chlorobenzene, or mixtures thereof, at a temperature of about 40°C and 130°C, for a period of time sufficient to essentially complete the reaction and yield a dialkyl quinoline-2,3-dicarboxylate.
- a hydrocarbon solvent such as toluene or a chlorinated hydrocarbon solvent such as methylene chloride, dichloroethane, ortho dischlorobenzene, chlorobenzene, or mixtures thereof
- the novel method of the present invention thus provides a simple and more efficient method for the production of anilinofumarate. This method, in turn, reduces handling, processing, effluent and solvents, resulting in a process that is cleaner, safer, cheaper and more efficient than prior reported methods.
- diethyl dichlorosuccinate (0.053 mol), which may be prepared by the method described in Japanese Patent 71 21, 564, is reacted with aniline (o.053 mol) by stirring the mixture in the presence of 0.08 molar equivalents of aqueous sodium carbonate (20% Na2CO3 w/w) and a catalytic amount (5 mol %) of tetrabutylammonium bromide at 95°C for two hours and 30 minutes.
- aniline o.053 mol
- the thus-formed anilinofumarate is readily isolated by separating off the organic phase from the aqueous slat phase.
- Aqueous bases suitable for the preparation of anilinofumarate by the present method include sodium and potassium hydroxide, carbonate and bicarbonate at concentrations of 15% to 50%, by weight, in amounts sufficient to provide about two molar equivalents.
- the carbonates being employed in from one to three molar equivalents and the hydroxides and bicarbonates being employed in from two to three molar equivalents.
- the quaternary ammonium phase transfer catalysts N-methyl-tri-n-butylammonium or tetra-n-butylammonium chloride, bromide and bisulfate, in amounts as little as 0.025 molar equivalent, have demonstrated comparable results and are preferred for the method of this invention.
- Chlorine gas is bubbled into an ethylene dichloride solution of diethyl maleate containing ethanol, (0.1 molar equivalents). After stirring the mixture at room temperature for eight hours, it is flushed with nitrogen gas for five minutes and the solvent removed under reduced pressure to yield the dichlorosuccinate in 94% yield.
- Tetra-n-butylammonium bromide (0.9g, 0.002% mol) is added to a 25% aqueous solution of sodium carbonate (8.5 g, 0.08 mol). Diethyl dichlorosuccinate (12.9 g real, 0.053 mol) is added at 20°C-25°C followed by aniline (4.5 g, 0.0483 mol). The reaction mixture is heated to 95°C over 30 minutes and held at this temperature for 1.7 hours. The phases are separated at 50°C-75°C. A portion of the solvent required for the next step can be added to increase the rate of this phase separation.
- the organic product phase is cooled to 25°C and washed with 8-10 g of 5% hydrochloric acid to remove excess aniline.
- the anilinofumarate product layer is dried by azeotropic distillation.
- aniline is reacted with diethyl dichlorosuccinate in the presence of sodium carbonate with various phase transfer catalysts, in both the presence or absence of an organic solvent at about 80°C to 95°C.
- the product is isolated and analyzed by gas chromatography (GC) in order to demonstrate the improvement obtained by the method of the present invention over prior methods.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Control Of Transmission Device (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT88113254T ATE85321T1 (de) | 1987-10-01 | 1988-08-16 | Verfahren zur herstellung von anilinofumaraten. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/101,453 US4814486A (en) | 1987-10-01 | 1987-10-01 | Method for the preparation of anilinofumarate |
| US101453 | 1987-10-01 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0309711A1 true EP0309711A1 (de) | 1989-04-05 |
| EP0309711B1 EP0309711B1 (de) | 1993-02-03 |
Family
ID=22284722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88113254A Expired - Lifetime EP0309711B1 (de) | 1987-10-01 | 1988-08-16 | Verfahren zur Herstellung von Anilinofumaraten |
Country Status (22)
| Country | Link |
|---|---|
| US (1) | US4814486A (de) |
| EP (1) | EP0309711B1 (de) |
| JP (1) | JP2703573B2 (de) |
| KR (1) | KR970006470B1 (de) |
| AR (1) | AR244658A1 (de) |
| AT (1) | ATE85321T1 (de) |
| AU (1) | AU611952B2 (de) |
| BG (1) | BG47347A3 (de) |
| BR (1) | BR8805058A (de) |
| CA (1) | CA1297126C (de) |
| CS (1) | CS275946B6 (de) |
| DD (1) | DD275453A5 (de) |
| DE (1) | DE3878122T2 (de) |
| ES (1) | ES2039525T3 (de) |
| GR (1) | GR3006960T3 (de) |
| HU (1) | HU200592B (de) |
| IE (1) | IE63235B1 (de) |
| IL (1) | IL87546A0 (de) |
| RO (1) | RO101205B1 (de) |
| RU (1) | RU1773259C (de) |
| YU (1) | YU45062B (de) |
| ZA (1) | ZA887372B (de) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0402561A2 (de) * | 1989-06-15 | 1990-12-19 | American Cyanamid Company | Verfahren zur Herstellung von Anilinofumarat via Chloromaleat oder Chlorofumarat oder Mischungen davon |
| WO2003080555A1 (fr) * | 2002-02-28 | 2003-10-02 | Sumitomo Chemical Company, Limited | Procede de production de compose chromone |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4910327A (en) * | 1982-05-25 | 1990-03-20 | American Cyanamid Company | Alkyl esters of substituted 2-methyl-3-quinolinecarboxylic acid and quinoline-2,3-dicarboxylic acid: dialkyl 3-(substituted)phenylaminobut-2-ene-dioates and methods for the preparation thereof |
| US5001254A (en) * | 1986-08-29 | 1991-03-19 | American Cyanamid Co | Novel method for the preparation of quinoline-2,3-dicarboxylic |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4675432A (en) * | 1986-08-29 | 1987-06-23 | American Cyanamid Company | Method for the preparation of anilinofumarate |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4638068A (en) * | 1981-04-09 | 1987-01-20 | American Cyanamid Company | 2-(2-imidazolin-2-yl)-pyridines and quinolines, process and intermediates for the preparation thereof, and use of said compounds as herbicidal agents |
| US4459409A (en) * | 1982-05-25 | 1984-07-10 | American Cyanamid Company | Process for the preparation of 2,3-quinolinedicarboxylic acids |
| US4656283A (en) * | 1982-05-25 | 1987-04-07 | American Cyanamid Company | Alkyl esters of substituted 2-methyl-3-quinolinecarboxylic acid and quinoline-2,3-dicarboxylic acid |
| US4518780A (en) * | 1982-05-25 | 1985-05-21 | American Cyanamid Company | Process for the preparation of 2-(5,5-disubstituted-4-oxo-2-imidazolin-2-yl)nicotinic acids and quinoline-3-carboxylic acids |
| ATE57912T1 (de) * | 1986-08-29 | 1990-11-15 | American Cyanamid Co | Verfahren zur herstellung von anilinofumarat und 2,3-chinolindicarbonsaeure. |
-
1987
- 1987-10-01 US US07/101,453 patent/US4814486A/en not_active Expired - Lifetime
-
1988
- 1988-08-16 EP EP88113254A patent/EP0309711B1/de not_active Expired - Lifetime
- 1988-08-16 AT AT88113254T patent/ATE85321T1/de not_active IP Right Cessation
- 1988-08-16 ES ES198888113254T patent/ES2039525T3/es not_active Expired - Lifetime
- 1988-08-16 DE DE8888113254T patent/DE3878122T2/de not_active Expired - Fee Related
- 1988-08-24 IL IL87546A patent/IL87546A0/xx not_active IP Right Cessation
- 1988-09-27 JP JP63239872A patent/JP2703573B2/ja not_active Expired - Lifetime
- 1988-09-27 RO RO1988135289A patent/RO101205B1/ro unknown
- 1988-09-29 DD DD88320260A patent/DD275453A5/de unknown
- 1988-09-29 CA CA000578776A patent/CA1297126C/en not_active Expired - Lifetime
- 1988-09-30 RU SU884356526A patent/RU1773259C/ru active
- 1988-09-30 BR BR8805058A patent/BR8805058A/pt not_active IP Right Cessation
- 1988-09-30 HU HU885099A patent/HU200592B/hu not_active IP Right Cessation
- 1988-09-30 YU YU1837/88A patent/YU45062B/xx unknown
- 1988-09-30 ZA ZA887372A patent/ZA887372B/xx unknown
- 1988-09-30 AU AU23304/88A patent/AU611952B2/en not_active Ceased
- 1988-09-30 KR KR1019880012832A patent/KR970006470B1/ko not_active IP Right Cessation
- 1988-09-30 AR AR88312093A patent/AR244658A1/es active
- 1988-09-30 CS CS886510A patent/CS275946B6/cs not_active IP Right Cessation
- 1988-09-30 IE IE296288A patent/IE63235B1/en not_active IP Right Cessation
- 1988-09-30 BG BG085574A patent/BG47347A3/xx unknown
-
1993
- 1993-02-04 GR GR920402264T patent/GR3006960T3/el unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4675432A (en) * | 1986-08-29 | 1987-06-23 | American Cyanamid Company | Method for the preparation of anilinofumarate |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0402561A2 (de) * | 1989-06-15 | 1990-12-19 | American Cyanamid Company | Verfahren zur Herstellung von Anilinofumarat via Chloromaleat oder Chlorofumarat oder Mischungen davon |
| EP0402561A3 (de) * | 1989-06-15 | 1991-05-29 | American Cyanamid Company | Verfahren zur Herstellung von Anilinofumarat via Chloromaleat oder Chlorofumarat oder Mischungen davon |
| AU617576B2 (en) * | 1989-06-15 | 1991-11-28 | American Cyanamid Company | Process for the manufacture of anilinofumarate via chloromaleate or chlorofumarate or mixtures thereof |
| WO2003080555A1 (fr) * | 2002-02-28 | 2003-10-02 | Sumitomo Chemical Company, Limited | Procede de production de compose chromone |
| US7094914B2 (en) | 2002-02-28 | 2006-08-22 | Sumitomo Chemical Company, Limited | Process for producing chromone compound |
| EP1867626A3 (de) * | 2002-02-28 | 2008-07-23 | Sumitomo Chemical Company, Limited | Procédé pour la préparation d'un dérivé de chromone |
| EP2105431A1 (de) * | 2002-02-28 | 2009-09-30 | Sumitomo Chemical Company, Limited | Verfahren zur Herstellung einer Chromonverbindung |
Also Published As
| Publication number | Publication date |
|---|---|
| AR244658A1 (es) | 1993-11-30 |
| JPH01113352A (ja) | 1989-05-02 |
| IE882962L (en) | 1989-04-01 |
| IE63235B1 (en) | 1995-04-05 |
| BG47347A3 (en) | 1990-06-15 |
| DE3878122D1 (de) | 1993-03-18 |
| HU200592B (en) | 1990-07-28 |
| YU45062B (en) | 1991-06-30 |
| CA1297126C (en) | 1992-03-10 |
| KR970006470B1 (ko) | 1997-04-28 |
| RU1773259C (ru) | 1992-10-30 |
| AU2330488A (en) | 1989-04-06 |
| DD275453A5 (de) | 1990-01-24 |
| BR8805058A (pt) | 1989-05-09 |
| KR890006570A (ko) | 1989-06-14 |
| HUT48573A (en) | 1989-06-28 |
| JP2703573B2 (ja) | 1998-01-26 |
| ATE85321T1 (de) | 1993-02-15 |
| DE3878122T2 (de) | 1993-05-27 |
| US4814486A (en) | 1989-03-21 |
| ES2039525T3 (es) | 1993-10-01 |
| CS8806510A2 (en) | 1991-07-16 |
| CS275946B6 (en) | 1992-03-18 |
| RO101205B1 (en) | 1992-01-28 |
| IL87546A0 (en) | 1989-01-31 |
| AU611952B2 (en) | 1991-06-27 |
| ZA887372B (en) | 1989-06-28 |
| GR3006960T3 (de) | 1993-06-30 |
| EP0309711B1 (de) | 1993-02-03 |
| YU183788A (en) | 1990-02-28 |
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